EP2551008A1 - Procédé et dispositif destinés à la génération de produits de lavage dans un lavage au gaz - Google Patents

Procédé et dispositif destinés à la génération de produits de lavage dans un lavage au gaz Download PDF

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Publication number
EP2551008A1
EP2551008A1 EP12004992A EP12004992A EP2551008A1 EP 2551008 A1 EP2551008 A1 EP 2551008A1 EP 12004992 A EP12004992 A EP 12004992A EP 12004992 A EP12004992 A EP 12004992A EP 2551008 A1 EP2551008 A1 EP 2551008A1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
gas
detergent
loaded
compressor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12004992A
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German (de)
English (en)
Inventor
Ulvi Kerestecioglu
Horst Weiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP2551008A1 publication Critical patent/EP2551008A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/20—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/308—Carbonoxysulfide COS
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to a process for the regeneration of a detergent, which is used at elevated pressure in a physical gas scrubbing for cleaning a hydrogen and carbon monoxide containing feed gas and thereby loaded with carbon dioxide and sulfur components and an apparatus for performing the method.
  • the scrubbed gas components are removed from the loaded detergent after gas washing, thereby regenerating the detergent.
  • the regenerated detergent is normally reused in gas scrubbing while the scrubbed gas components are either disposed of or recycled for commercial use.
  • carbonaceous feedstocks are converted by gasification into a synthesis crude gas according to the prior art.
  • a synthesis gas also contains, in addition to the desired constituents hydrogen and carbon monoxide, a number of undesirable constituents, such as carbon dioxide (CO 2 ), hydrogen sulphide (H 2 S) and carbon dioxide sulphide (COS).
  • CO 2 carbon dioxide
  • H 2 S hydrogen sulphide
  • COS carbon dioxide sulphide
  • the crude synthesis gas is preferably subjected to physical gas scrubbing.
  • Such a method lends itself to this, since the synthesis gas is produced today usually under high pressure and the effectiveness of a physical gas scrubbing linearly increases in line with the operating pressure.
  • the methanol wash Of particular importance for the purification of synthesis gas is the methanol wash. She takes advantage of the fact that the Solubility coefficients of undesirable components in cryogenic methanol are several orders of magnitude greater than those of H 2 and CO. Since the solubility coefficients of carbon dioxide and the sulfur components H2S and COS greatly increase with decreasing temperature, the methanol detergent is usually introduced at a temperature which is far below 0 ° C in an absorber column and brought into intensive contact with the synthesis gas to be purified. The loaded with undesirable components methanol is regenerated after the washing process and returned to the washing process.
  • the loaded methanol detergent of the prior art is withdrawn from the absorber column and a so-called.
  • Enrichment column which is a stripping column, abandoned in its upper region.
  • a countercurrent stripping gas which is usually nitrogen, predominantly CO 2 from the methanol detergent, whereby the sulfur components accumulate.
  • the cold generated during the CO 2 exhaustion is used to reduce the inevitable cold losses of a methanol wash.
  • the gas mixture withdrawn from the head of the enrichment column and consisting predominantly of CO 2 and stripping gas can be generally distilled off. not be used economically, which is why it is disposed of subsequently.
  • One way of disposal is to release the gas mixture into the atmosphere, but this is increasingly considered problematic in terms of global warming.
  • the transfer of the gas mixture into deep layers of the earth or its use in the exploitation of oil wells (Enhanced Oil Recovery).
  • its nitrogen content is limited to low levels of less than about 4 mol%, so that the use of nitrogen as stripping gas, as is currently the case, prohibits.
  • Object of the present invention is therefore to provide a method of the generic type and a device for their implementation in such a way that overcomes the disadvantages of the prior art.
  • This object is achieved in that loaded with carbon dioxide and sulfur components detergent to a pressure between 0.4 and 1.7bar (a), preferably between 1.0 and 1.3 bar (a) and depressurized released during the expansion carbon dioxide-rich, sulfur components containing gas is compressed and introduced into a wash column in which sulfur components from the carbon dioxide-rich gas with the aid of sulfur-free detergent are washed.
  • the carbon dioxide-rich gas is usefully introduced into the lower section of the scrubbing column where it is passed upwards in countercurrent to sulfur-free detergent.
  • the sulfur-free detergent is preferably a detergent saturated with carbon dioxide, which is specifically loaded with carbon dioxide during the purification of the feed gas, which has already been largely freed from sulfur components.
  • sulfur-rich gas contained sulfur components are absorbed by the sulfur-free detergent, while carbon dioxide largely remains in the gas phase.
  • the concentration of carbon dioxide remaining in the loaded detergent is essentially determined by the pressure to which the detergent is depressurized. By relaxing to pressures near or below ambient, the carbon dioxide content of the loaded detergent can be reduced to very low levels. At the same time, the separated carbon dioxide can be prepared in the wash column in any purity and released as a product and used for example for enhanced oil recovery.
  • the process according to the invention can be used for the regeneration of any desired detergent.
  • it is particularly advantageously used in the regeneration of charged methanol or N-methylpyrrolidone (NMP) or polyethylene glycol dimethyl ether (PEGE).
  • the invention relates to a device for regenerating a detergent, which is used at elevated pressure in a physical gas scrubbing for cleaning a hydrogen and carbon monoxide-containing feed gas and thereby loaded with carbon dioxide and sulfur components.
  • the device comprises a throttle body and a flash vessel and a washing column, both of which are connected via a compressor, whereby laden detergent via the throttle body in the expansion vessel is relaxed and released during the relaxation of gas with the help of the compressor can be compressed and introduced into the wash column.
  • the invention provides a upstream of the throttle body arranged pump through which the pressure prevailing in front of the throttle body of the loaded detergent can be raised.
  • the first container can also be arranged offset upwards relative to the second container and the throttle element, so that the hydrostatic pressure of the detergent upstream of the throttle element can be increased.
  • an embodiment of the invention provides a arranged between the compressor and the scrubber heat exchanger, via the compressed gas before his Initiation in the wash column can be cooled, for example with cooling water.
  • the scrubbing column and the expansion vessel or vessels can be designed as separate components or as a structural unit.
  • FIG. 1 schematically illustrated embodiment.
  • FIG. 1 shows a section of a physical gas scrubber in which carbon dioxide and sulfur components are washed out of a synthesis gas with the aid of liquid and cryogenic methanol.
  • the synthesis gas to be washed which also contains carbon dioxide and sulfur components in addition to hydrogen and carbon monoxide, is introduced via line 1 into the heat exchanger E1 and cooled there against process streams to be heated, before it can be fed via line 2 of the absorber column A in its lower part.
  • the absorber column A which is typically at a pressure is operated between 15 and 80 bar, has a lower S1 and an upper washing section S2, which are separated by a chimney tray K1.
  • the cold synthesis crude gas is conducted upwards in the absorber column A and brought into intensive contact with methanol washing agent, which is introduced into the scrubbing section S2 unloaded via line 3.
  • the mass flow of the methanol detergent is adjusted via the control element a so that carbon dioxide is substantially completely or washed out to a desired degree from the synthesis gas.
  • About the lines 4 and 5 and the control element b pre-loaded with carbon dioxide methanol detergent is forwarded to the washing section S1, where it mainly absorbs sulfur components from the synthesis crude because of its flow, before it is loaded with carbon dioxide and sulfur components from the bottom space of the column A and over Line 6 is continued.
  • a gas 7 consisting largely of hydrogen and carbon monoxide can be withdrawn, which gas is released as synthesis gas product 8 after being heated against the synthesis crude 1.
  • the loaded methanol streams 4 and 6 are expanded via the throttle elements c and d into the separators D1 and D2.
  • the gas phases formed in this case which predominantly consist of hydrogen and carbon monoxide co-absorbed in the gas scrubbing, are returned to the synthesis raw gas 1 via the lines 9, 10 and 11 and the compressor V1.
  • the loaded methanol 12 is withdrawn from the separator D2 and relaxed via the throttle member e in the middle part of the typically operated between 3 and 4.5 bar medium pressure column M.
  • the second part 18 of the sulfur-free is at the top of the scrubbing column W loaded methanol stream 14 introduced via the throttle body h.
  • the pump P from the chimney tray K3 of the scrubbing column W is rich in sulfur components, but still containing carbon dioxide methanol withdrawn via line 19 and introduced into the bottom space of the medium-pressure column M, after it in the heat exchangers E2 and E3 against regenerated 3 or loaded methanol 4 was warmed.
  • By heating a portion of the carbon dioxide contained is expelled from the methanol, which is discharged at a higher pressure at the top of the medium-pressure column M with the stream 15.
  • the further loaded with sulfur and residues of carbon dioxide detergent is withdrawn via line 20 from the bottom space of the medium-pressure column M and relaxed via the throttle body i in the lower part of the wash column W, wherein a further portion of the dissolved carbon dioxide is released.
  • the sulfur-rich methanol 21 is withdrawn from the wash column W and passed through the throttle member j in the flash vessel B, which forms a structural unit with the wash column W. Due to the pressure prevailing here, which may be below atmospheric pressure, a carbon dioxide-rich gas phase containing sulfur components and a methanol enriched with sulfur components, which is greatly reduced in carbon dioxide, is formed.
  • the carbon dioxide products 16 and 25 are fed to a compressor unit (not shown) and can be used, for example, for enhanced oil recovery.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Industrial Gases (AREA)
EP12004992A 2011-07-26 2012-07-05 Procédé et dispositif destinés à la génération de produits de lavage dans un lavage au gaz Withdrawn EP2551008A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102011108530A DE102011108530A1 (de) 2011-07-26 2011-07-26 Verfahren und Vorrichtung zur Waschmittelregenerierung in Gaswäschen

Publications (1)

Publication Number Publication Date
EP2551008A1 true EP2551008A1 (fr) 2013-01-30

Family

ID=46545598

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12004992A Withdrawn EP2551008A1 (fr) 2011-07-26 2012-07-05 Procédé et dispositif destinés à la génération de produits de lavage dans un lavage au gaz

Country Status (8)

Country Link
US (1) US20130025452A1 (fr)
EP (1) EP2551008A1 (fr)
JP (1) JP2013028805A (fr)
CN (1) CN102895849A (fr)
AU (1) AU2012207039A1 (fr)
BR (1) BR102012018377A2 (fr)
CA (1) CA2783049A1 (fr)
DE (1) DE102011108530A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3620224A1 (fr) * 2018-09-07 2020-03-11 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Procédé d'élimination des composants gazeux acides du gaz de synthèse et dispositif de production de gaz de recyclage

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013001677A1 (de) * 2013-01-31 2014-07-31 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Erzeugung von Brennstoff für eine Gasturbine
DE102014018844A1 (de) * 2014-12-17 2016-06-23 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Waschmittelregenerierung in einer physikalischen Gaswäsche
DE102015013796A1 (de) * 2015-10-22 2017-04-27 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung von Gasprodukten
EP3616775B1 (fr) * 2018-09-03 2024-05-01 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Dispositif de séparation des métaux carbonyles à partir de gaz brut de synthèse

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0012986A1 (fr) * 1978-12-23 1980-07-09 Linde Aktiengesellschaft Procédé pour la séparation et la récupération de composants gazeux à partir d'un mélange de gaz par lavage physique
US4780115A (en) * 1986-04-18 1988-10-25 Linde Aktiengesellschaft Process for removing undesirable components from gases
WO2010057581A1 (fr) * 2008-11-19 2010-05-27 Linde Aktiengesellschaft Procédé et appareillage pour la régénération du produit de lavage lors du lavage physique des gaz
EP2223889A2 (fr) * 2009-02-25 2010-09-01 Linde Aktiengesellschaft Dispositif de conversion de carburants solides ou liquides dans un carburant gazeux

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2548700C2 (de) * 1975-10-30 1982-04-01 Linde Ag, 6200 Wiesbaden Verfahren und Vorrichtung zur Wasserstoffreinigung unter gleichzeitiger Kohlendioxidgewinnung
DE3047830A1 (de) * 1980-12-18 1982-07-15 Linde Ag, 6200 Wiesbaden Verfahren zum reinigen eines gasstromes
DE3148520A1 (de) * 1981-12-08 1983-07-21 Linde Ag, 6200 Wiesbaden "verfahren zur entfernung von sauren gasen aus gasgemischen"
DE3343916A1 (de) * 1983-12-05 1985-06-13 Linde Ag, 6200 Wiesbaden Verfahren und vorrichtung zum regenerieren eines loesungsmittels
DE102010013279B3 (de) * 2010-03-29 2011-07-28 Uhde GmbH, 44141 Verfahren und Vorrichtung zur Verarbeitung eines kohlendioxidreichen Sauergases in einem Claus-Prozess

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0012986A1 (fr) * 1978-12-23 1980-07-09 Linde Aktiengesellschaft Procédé pour la séparation et la récupération de composants gazeux à partir d'un mélange de gaz par lavage physique
US4780115A (en) * 1986-04-18 1988-10-25 Linde Aktiengesellschaft Process for removing undesirable components from gases
WO2010057581A1 (fr) * 2008-11-19 2010-05-27 Linde Aktiengesellschaft Procédé et appareillage pour la régénération du produit de lavage lors du lavage physique des gaz
EP2223889A2 (fr) * 2009-02-25 2010-09-01 Linde Aktiengesellschaft Dispositif de conversion de carburants solides ou liquides dans un carburant gazeux

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3620224A1 (fr) * 2018-09-07 2020-03-11 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Procédé d'élimination des composants gazeux acides du gaz de synthèse et dispositif de production de gaz de recyclage
CN110882606A (zh) * 2018-09-07 2020-03-17 乔治洛德方法研究和开发液化空气有限公司 用于从合成气去除酸性气体成分的方法及用于产生再循环气体的装置
US10874977B2 (en) 2018-09-07 2020-12-29 L'air Liquide Societe Anonyme Pour L'etude Et L'explotation Des Procedes Georges Claude Process for removal of acidic gas constituents from synthesis gas and apparatus for producing recycle gas
CN110882606B (zh) * 2018-09-07 2023-08-15 乔治洛德方法研究和开发液化空气有限公司 用于从合成气去除酸性气体成分的方法及用于产生再循环气体的装置

Also Published As

Publication number Publication date
AU2012207039A1 (en) 2013-02-14
DE102011108530A1 (de) 2013-01-31
JP2013028805A (ja) 2013-02-07
CN102895849A (zh) 2013-01-30
US20130025452A1 (en) 2013-01-31
CA2783049A1 (fr) 2013-01-26
BR102012018377A2 (pt) 2013-07-30

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